CN101825734B - Phase difference film and manufacturing method thereof - Google Patents
Phase difference film and manufacturing method thereof Download PDFInfo
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- CN101825734B CN101825734B CN201010127064.XA CN201010127064A CN101825734B CN 101825734 B CN101825734 B CN 101825734B CN 201010127064 A CN201010127064 A CN 201010127064A CN 101825734 B CN101825734 B CN 101825734B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/91—Product with molecular orientation
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Abstract
The invention relates to a phase difference film and manufacturing method thereof and provides the phase difference film which has regulated delay values, high transparent property and excellent heat-resistant property of the phase difference. The manufacturing method of the phase difference film comprises that resin compositions containing prescribed silicon resin (1), optical polymerization initiator (2) and / or heat polymerization initiator (3) by the phase difference film are cured, the phase difference value variation amount of the phase difference film after being heated for 10 hours is 0-20 nm phase difference film. The method can enable the unsaturated groups of the resin compositions to be reduced to 0.1-50% primary curing to obtain a resin forming body, then the resin forming body is cut into the regulated shape and is fixed on a drawing clamp, he resin forming body is drawn in any direction by the range of 5-700% drawing multiplying factor to obtain a drawing resin forming body, under the state of fixing the drawn resin forming body on the drawing clamp, the energy ray can be further heated and /or irradiated thereto to enable the drawn resin forming body to be performed for the secondary curing, and then to be cooled to the room temperature.
Description
Technical field
The present invention relates to phase retardation film and manufacture method thereof, in detail, even if relate to also phase retardation film and the manufacture method thereof few, that there is excellent properties of variable quantity with phase differential after high transparent heating.
Background technology
In recent years, be widely used the CRT that liquid crystal indicator replaces Braun tube mode.In these liquid crystal indicators, for removal of images is painted or in order to expand visual angle, use phase retardation film.In addition,, in projection type projector, laser beam splitter, use the mutual conversion element of phase retardation film as linear polarization and rotatory polarization.And then, in the purposes of touch panel, make visual raising in order to reduce outside reflection of light, require to import phase retardation film.
These phase retardation films are the films that adopt the birefringence material of the phase contraposition phase of the composition for changing the light after polarisation to make, and plastic alignment films is generally used as birefringence layer.As the structure of phase retardation film; there are the single layer structure being formed by 1 birefringence layer, sandwich construction and the structure with protective seam etc. (for example,, with reference to patent documentation 1) that identical or different birefringence 2 layers above birefringent layers are laminated.
For example, liquid crystal display in order to obtain distinct color and image clearly, must have following characteristic with phase retardation film: the whole face of birefringence layer is all optically uniformly, even and if temperature and humidity changes, optical characteristics does not also change.Carry in the liquid crystal display, panel of use during especially for automobile, use owing to predicting under critical conditions, require heat resisting temperature be at least 60 DEG C above, preferably 80 DEG C above, more preferably more than 100 DEG C.But, phase retardation film up to now, main as the polycarbonate resin (for example,, with reference to patent documentation 2) of thermoplastic resin, norbornene resin (for example utilization, with reference to patent documentation 3), cannot obtain enough thermotolerances and weatherability.
In addition, in the time adopting the high thermoplastic resin of glass transition temperature (Tg), generally manufacture sheet by solution casting method, although the surface smoothness excellence of the film after stretch orientation, but production rate variance, in addition, have the problem that cannot use according to the difference of environment for use owing to there being dissolvent residual.
[patent documentation 1] Unexamined Patent 5-2108 communique
[patent documentation 2] JP 2006-143831 communique
[patent documentation 3] JP 2006-301522 communique
[patent documentation 4] WO2008/123347 communique
Summary of the invention
Therefore, even if the object of the present invention is to provide also phase retardation film and the manufacture method thereof few, that there is excellent properties of variable quantity with phase differential after high transparent and heating.
Although present inventors etc. have proposed the phase retardation film of above-mentioned patent documentation 4, but to achieve these goals, conduct in-depth research, found that: the resin combination that contains specific silicon resin by use, even if the phase differential that can obtain having high transparent and heating rear rheological parameters' change with time reduces the phase retardation film of further being improved, thereby has completed the present invention.
; the present invention relates to phase retardation film; it is characterized in that; to make resin combination solidify the phase retardation film forming; the scope that is 0～20nm at 100 DEG C of phase difference value variable quantities that carry out 10 hours phase retardation films after heat treated, described resin combination contains the represented number-average molecular weight of (1) following general formula (1) silicones and (2) Photoepolymerizationinitiater initiater and/or (3) thermal polymerization in 1000～80000 scopes.
(in formula, X is the divalent group with at least one silicon atom and at least one aromatic group, R
1the organo-functional group with (methyl) acryloyl group, R
2represent to have replacement or unsubstituted aromatic rings that the organo-functional group of (methyl) acryloyl group or vinyl, aliphatic hydrocarbon that carbon number is 1～25, replacement that carbon number is 6～15 or unsubstituted alicyclic ring or carbon number are 6～15, l=1, m=1～3, n are 2～290.〕
In addition, the present invention relates to the manufacture method of phase retardation film, it is characterized in that, use resin combination to manufacture phase retardation film, described resin combination contains the represented number-average molecular weight of (1) following general formula (1) silicones and (2) Photoepolymerizationinitiater initiater and/or (3) thermal polymerization in 1000～80000 scopes
(in formula, X is the divalent group with at least one silicon atom and at least one aromatic group, R
1the organo-functional group with (methyl) acryloyl group, R
2represent to have replacement or unsubstituted aromatic rings that the organo-functional group of (methyl) acryloyl group or vinyl, aliphatic hydrocarbon that carbon number is 1～25, replacement that carbon number is 6～15 or unsubstituted alicyclic ring or carbon number are 6～15, l=1, m=1～3, n are 2～290.〕
In the method, with at least 1 supporting mass supporting resin combination, the one-step solidification of the unsaturated group minimizing 0.1%～50% of above-mentioned by making (1) composition obtains after resin-formed body, this resin-formed body is cut into regulation shape and is fixed on stretching clamp, after stretching with the scope of stretching ratio 5～700% in any direction, obtain stretching resin formed body, under the state that this stretching resin formed body is fixed on to stretching clamp, further heat and/or irradiation energy ray and make it regelate, then cool to room temperature.
In the present invention, form the resin combination of phase retardation film contain the represented number-average molecular weight of following general formula (1) at the silicones of 1000～80000 scopes as (1) composition.
(in formula, X is the divalent group with at least one silicon atom and at least one aromatic group, R
1the organo-functional group with (methyl) acryloyl group, R
2represent to have replacement or unsubstituted aromatic rings that the organo-functional group of (methyl) acryloyl group or vinyl, aliphatic hydrocarbon that carbon number is 1～25, replacement that carbon number is 6～15 or unsubstituted alicyclic ring or carbon number are 6～15, l=1, m=1～3, n are 2～290.〕
The silicones of using as (1) composition can be manufactured by normally used method.Be, to carry out synthetic method etc. by polyol, dichlorosilane compound and the compound endways with polymerism unsaturated group and hydroxyl.Now, can be by the silicones using in resin combination of the present invention that mole recently obtains in the molecular weight of suitable adjusting raw material or when reaction.
As above-mentioned polyol, be advisable with the silicon compound that there are 2 hydroxyls and there is at least one aromatic group in 1 molecule, for example, to there are 2 silanol groups and there are one or more compound can with substituent aromatic rings, specifically Isosorbide-5-Nitrae-bis-(hydroxyl dimetylsilyl) benzene etc., in addition, for example, be the dihydroxy silane that there is at least one and can have substituent aromatic group, specifically can illustrate diphenyl silanodiol etc.
In addition,, as dichlorosilane compound, can enumerate dimethyldichlorosilane, acetoxyl group propyl group dimethyl dichlorosilane (DMCS), (3-acryloxy propyl group) dimethyl dichlorosilane (DMCS), allyl methyl dichlorosilane, allyl phenyl dichlorosilane, two [2-(Chlorodimethyl silicyl ethyl) benzene, two (the chloromethyl dimethyl silane oxygen base) benzene of 1,3-, butenyl group dimethyl dichlorosilane (DMCS), tert-butyl group dimethyl dichlorosilane (DMCS), tert-butyl-phenyl dichlorosilane, 2-(methoxycarbonyl base) ethyl-methyl dichlorosilane, [(chloromethyl) phenylethyl] dimethylchlorosilane, [2-(3-cyclohexenyl group) ethyl] dimethyl dichlorosilane (DMCS), chlorine hexyl methyl dichlorosilane, ring tetramethylene dichlorosilane, benzyloxy dichlorosilane, 1,3-bis-is chloro-1,3-diphenyl-1,3-dimethyldichlorosilane, 1,5-dichloro hexam ethylcyclotrisiloxane, 1,7-dichloro octamethylcyclotetrasiloxane, 1,3-dichloro tetramethyl disiloxane, 1,3-dichloro tetraphenyl disiloxane, dicyclohexyl dichlorosilane, diphenyl dichlorosilane, two (p-methylphenyl) dichlorosilane, divinyl dichlorosilane, ethyl-methyl dichlorosilane, methacryloxypropyl dichlorosilane, 3-(p-methoxyphenyl) propyl group dimethyl dichlorosilane (DMCS), phenylmethyldichloroislane, phenylmethyldichloroislane, 1,1,3,3-Fourth Ring amyl group dichloro disiloxane, p-methylphenyl dimethyl dichlorosilane (DMCS), (3,3,3-trifluoro propyl) dimethyl dichlorosilane (DMCS), vinyl dimethyl dichlorosilane (DMCS), ethenylphenyl dichlorosilane, divinyl dichlorosilane, dichloromethyl phenylsilane, Isosorbide-5-Nitrae-bis-(dimethyl chloride silicyl) benzene, 1,1,3,3,5,5-vegolysen, 5-dichloro trisiloxanes, 1,7-bis-is chloro-1,1,3,3,5,5,7,7-octamethylcyclotetrasiloxane etc.
As the compound endways with polymerism unsaturated group and hydroxyl, for example can enumerate (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-2-hydroxyl-3-phenoxy group propyl ester, 2-(methyl) acryloxy ethyl-2-hydroxyethyl phthalic ester, pentaerythrite three (methyl) acrylate, 3-acryloyl-oxy base glycerol list (methyl) acrylate, (methyl) acrylic acid-2-hydroxy butyl ester, 2-hydroxyl-1-(methyl) acryloxy-3-(methyl) acryloxy propane, glycerine two (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polyethyleneglycol (methyl) acrylate, poly-epsilon-caprolactone list (methyl) acrylate, (methyl) acrylic acid-4-hydroxy butyl ester, 6-caprolactone list (methyl) acrylate, various epoxy acrylates etc.
Obtain the method that the condition of silicones of the present invention is preferably as follows: at ambient temperature, in reaction system, add with react in the hydrogen chloride that produces for etc. mole or more alkali compounds, by the mol ratio Molecular regulator amount of polyol and dichlorosilane compound, be added in end and have the method for the compound of polymerism unsaturated group and hydroxyl.The mol ratio of polyol and dichlorosilane compound more approaches 1: 1, more can obtain high molecular body.Polyol, dichlorosilane compound and the compound endways with polymerism unsaturated group and the hydroxyl mol ratio in the time of reaction preferably 10: 15: 4, more preferably 20: 21: 4.
In addition, in resin combination of the present invention, coordinate (2) Photoepolymerizationinitiater initiater and/or (3) thermal polymerization as radical polymerization initiator.In the time only coordinating (2) Photoepolymerizationinitiater initiater, its addition is with respect to total 100 weight portions of resin combination, and (2) Photoepolymerizationinitiater initiater is preferably the scope of 0.1～3 weight portion.In the time only coordinating (3) thermal polymerization, with respect to total 100 weight portions of resin combination, its addition is preferably the scope of 0.1～10 weight portion.In the time coordinating (2) Photoepolymerizationinitiater initiater and (3) thermal polymerization, with respect to total 100 weight portions of resin combination, preferably (2) Photoepolymerizationinitiater initiater is that 0.01～1 weight portion, (3) thermal polymerization are the scope of 0.01～10 weight portion.In each cooperation, while being less than above-mentioned scope due to crosslinked insufficient the fixing of stretch orientation that be difficult to carry out, even and if content exceedes the raising that above-mentioned scope also cannot expected response rate.
As above-mentioned (2) Photoepolymerizationinitiater initiater, can preferably use the compounds such as acetophenone system, benzoyl system, benzophenone series, thioxanthones system, acylphosphine oxide system.Specifically can illustrate trichloroacetophenone, diethoxy acetophenone, 1-phenyl-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone, benzoin methylether, benzil dimethyl ketal, benzophenone, thioxanthones (チ オ キ サ Application ソ Application), 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide, aminomethyl phenyl glyoxylic ester, camphorquinone, benzil, anthraquinone, michaelis ketone etc.In addition, can also and use light-initiated auxiliary agent, the sensitizer of performance effect with Photoepolymerizationinitiater initiater combination.
As above-mentioned (3) thermal polymerization, can enumerate the known organic peroxide and the azo-compound etc. that are categorized into ketone peroxide, ketal peroxide, hydrogen peroxide, diallyl superoxide, diacyl peroxide, peroxyester, peroxy dicarbonate.As concrete example, can enumerate benzoyl peroxide, dicumyl peroxide, diisopropyl superoxide, di-tert-butyl peroxide, peroxidized t-butyl perbenzoate, 1, two (tert-butyl hydroperoxide)-3 of 1-, 3, 5-trimethyl-cyclohexane, 2, 5-dimethyl-2, two (tert-butyl hydroperoxide) hexin-3 of 5-, 3-hyperis, tert-butyl hydroperoxide, dicumyl peroxide, dicumyl hydrogen peroxide, acetyl peroxide, two (4-tert-butylcyclohexyl) peroxy dicarbonate, di-isopropyl peroxydicarbonate, isobutyl peroxide, 3, 3, 5-trimethyl acetyl base superoxide, lauryl peroxide, azoisobutyronitrile, azobisformamide etc.
Resin combination of the present invention is except the composition of above-mentioned (1)～(3), in the scope not reducing as the function of phase retardation film, can contain the resin at least with 1 energy and the unsaturated group of aforementioned (1) composition generation free radical polymerization.For this composition, with have unsaturated group ester ring type monomer, there is the aliphatic monomer of unsaturated group or have containing the substituent cage-type silsesquioxane of unsaturated group and be advisable, the potpourri that can use a kind in them or two or more is mixed.As its example, can enumerate cage-type silsesquioxane, tetrahydro-dicyclopentadiene base diacrylate, trimethylol-propane trimethacrylate, tripropylene glycol diacrylate, 1,6-hexanediyl ester, bisphenol A diglycidyl ether diacrylate, tetraethylene glycol diacrylate, 3-hydroxypivalic acid neopentylglycol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate etc.
And then, except the composition of above-mentioned (1)～(3), in the scope not reducing as the function of phase retardation film, can also add various adjuvants.As various adjuvants, can illustrate organic/inorganic filler, plastifier, fire retardant, thermal stabilizer, antioxidant, light stabilizer, ultraviolet light absorber, lubricant, antistatic agent, release agent, gas-development agent, nucleator, colorant, crosslinking chemical, dispersing aid, resinous principle etc.
In the present invention, the manufacture process of phase retardation film is as follows.That is, make resin combination one-step solidification and obtain resin-formed body, then making it to be orientated by this resin-formed body that stretches.Then, make the stretching resin formed body regelate of gained and obtain phase retardation film.Wherein, when making resin combination one-step solidification and obtaining the resin-formed body of part generation free radical polymerization, as the method, can enumerate heating means or energy-ray illuminating method, wherein, for heating means, with 25～200 DEG C, preferably the scope of 25～180 DEG C is heated to be suitable, on the other hand, for energy-ray method, preferably irradiate electron beam, ultraviolet ray, the visible ray homenergic ray of 300～6000mj.
While making it one-step solidification by irradiation ultraviolet radiation, visible ray homenergic ray, for example can adopt with the following method: multiple supporting masses are assembled and at least 1 supporting mass be to see through resin by injection composition in the mould that ultraviolet transparent raw material forms with quartz glass etc., use UV-lamp irradiation ultraviolet radiation, utilize the polymerizing curable that at least carries out accommodated resin combination by the ultraviolet ray of transparent raw material, then make it the demoulding from mould, obtain thus the resin-formed body of required form.In addition, during without mould, can also illustrate and for example use steel band as supporting mass, with spreader coating resin composition on mobile steel band of scraper or roller shape, make it polymerizing curable by above-mentioned UV-lamp, obtain thus the method for the resin-formed body of sheet etc.In addition, for heating means, the resin combination that injects the resin combination in mould or coat on steel band is heated in the temperature range of regulation.
While carrying out the one-step solidification of resin combination by irradiation energy ray, preferably obtain resin-formed body by the ultraviolet ray of illumination wavelength 10～400nm or the luminous ray of wavelength 400～700nm.The light wavelength using is not particularly limited, the particularly preferably near ultraviolet ray of wavelength 200～400nm.As the lamp as ultraviolet generation source, can illustrate low pressure mercury lamp (power: 0.4～4W/cm), high-pressure sodium lamp (40～160W/cm), ultrahigh pressure mercury lamp (173～435W/cm), metal halide lamp (80～160W/cm), pulse xenon lamp (80～120W/cm), electrodeless discharge lamp (80～120W/cm) etc.
In addition, while obtaining resin-formed body by one-step solidification, be made as following mode, that is, make it to carry out one-step solidification to reduce 0.1%～50% until the unsaturated group of above-mentioned (1) composition adds up to.In order to control the slip (following, be called " reaction rate ") of unsaturated group, preferably adjust heating condition, or adjust the exposure of lamp.While adopting irradiation energy ray, can determine exposure scope according to the kind of used lamp and resin combination.For example, in the time being ultrahigh pressure mercury lamp (333W/cm), can regulate arbitrarily exposure to obtain required reaction rate by the scope at 400～6000mj.In addition, although the adjusting of exposure can be adjusted by irradiation time, when but irradiation time is too short, cannot obtain the repeatability of reaction rate, and irradiation time throughput rate variation when long, therefore preferably pass through used lamp or device is suitably adjusted.On the other hand, adopt when heating means, to heat up and to be advisable gradually near room temperature, the heat time is according to the kind of thermal polymerization and resin combination and different, is advisable with about 20 points of kind～4 hour.
When the reaction rate of the resin-formed body after one-step solidification is too low, be difficult to retention tab shape, likely easily fracture, on the contrary, when too high, stretching ratio is low, cannot obtain required high phase difference value.Therefore, preferred reaction rate is 0.1%～50%, more preferably 0.1%～30% scope.
The thickness of the resin-formed body so obtaining is not particularly limited, and can suitably determine according to the application target of gained stretched film (phase retardation film) etc.In general, from adopting stable stretch processing to obtain the viewpoint grade of homogeneous stretched film, be preferably thick membranaceous of 5～500 μ m.
In the present invention, make by stretching to adopt the resin-formed body that said method obtains to be orientated, can obtain presenting the phase retardation film of birefringence.That is, resin-formed body obtained above is cut into regulation shape, is fixed on stretching clamp, obtain stretching resin formed body by stretching.By the resin-formed body obtained above that stretches, make resin-formed body stretch orientation and present birefringence.As the method for stretch orientation, can adopt the uniaxial tensions such as such as free wide cut uniaxial tension, constant wide cut uniaxial tension, biaxial stretch-formed, simultaneously biaxial stretch-formed etc. biaxial stretch-formed etc. successively, preferably carry out uniaxial tension in wide cut direction.In addition, be not particularly limited for the stretching clamp of the resin-formed body for being fixedly cut into regulation shape, can or there are stable on heating plastics to metals such as such as iron, aluminium, copper, brass and process rear use.This resin-formed body that can not succeed in reaching an agreement overstretching to generate has sufficient rigidity with regard to counter stress.
Temperature during by resin-formed body stretch orientation, according to the elastic modulus being obtained by the Measurement of Dynamic Viscoelasticity of resin-formed body and different, in order to reduce the residual stress after stretching, with show elastic modulus preferably 1000～0.01Mpa, more preferably the temperature range of 100～0.1Mpa scope is advisable.
When draw speed during by resin-formed body stretch orientation diminishes, due to heat fade, phase difference value reduces, or easily fracture in follow-up regelate operation.Therefore, more than the preferred 1mm/ of draw speed minute.But film can rupture when too fast, or fixture in stretching device comes off, therefore the more preferably scope of 1mm/ minute～10mm/ minute.
In addition, in the time that being stretched, resin-formed body can obtain required phase difference value by adjusting stretching ratio.In the manufacture method of phase retardation film of the present invention, be made as in 5～700% scope, preferably 5～500% scope stretches.Extensibility lower than 5% time, is difficult to present phase differential, and on the contrary, higher than 500% time, film likely ruptures.
So carry out the film of uniaxial tension for the orientation of fixing film, adopted following any means to carry out regelate.That is, this stretching resin formed body is being fixed under the state of stretching clamp, is further heating and/or irradiation energy ray and make it regelate, making reaction rate be roughly 100%, curing reaction is finished.
As the first method, with the state that keeps the stretching wide cut after stretching, stretching resin formed body is fixed on stretching clamp, and under this state, keeps stipulated time, set point of temperature to be advisable.Temperature is now more than draft temperature and can in the wide region of DEG C front and back, room temperature～200, selects according to the selection of thermal polymerization.In addition, the time of maintenance was advisable with 20 minutes～4 hours.Now, the stretching clamp of fixing stretching resin formed body preferably has the mechanism of the tension force of the fixture fixing for being adjusted into maintenance stretching wide cut.When tension force is too low, because the orientation mitigation due to heat is large to the contraction of draw direction, cannot fully keep the orientation after stretching.On the contrary, when too high, occur, because of the fracture due to cure shrinkage, to be difficult to carry out the making of film.Be cooled to room temperature by so having carried out heat treated film with the state that keeps stretching wide cut.
As the second method, with the state of stretching wide cut after keeping stretching, stretching resin formed body is fixed on stretching clamp, and under this state with the scope irradiation energy ray of 3000mj～20000mj.
As third method, with the state that keeps the stretching wide cut after stretching, stretching resin formed body is fixed on stretching clamp, and after the scope irradiation energy ray with 3000mj～20000mj, keeps stipulated time, set point of temperature to be advisable under this state.Temperature is now identical with the situation of the first method with the retention time.By irradiation energy ray, fracture strength is increased, can suppress the fracture in regelate.So carry out heat treated film cool to room temperature under the state that keeps stretching wide cut.
As cubic method, as required, in at least one side of the stretching resin formed body after can stretching resin formed body or regelate before regelate, coating is containing the curable resin of Photoepolymerizationinitiater initiater state, irradiate the energy-ray of 1000～20000mj, thereby form light-cured resin layer.; stretching resin formed body is being taken off from stretching clamp or be fixed under the state of stretching clamp; on the curable resin that contains Photoepolymerizationinitiater initiater is coated at least simultaneously; irradiate above-mentioned energy-ray and form the light-cured resin layer of at least 1 layer, stretching resin formed body can be fixed thus.The method can be used as the householder method of the method that uses stretching clamp.
As the 5th method, as required, in at least one side of the stretching resin formed body after can stretching resin formed body or regelate before regelate, coating is containing the curable resin of thermal polymerization state, at the temperature of 25～200 DEG C, carry out the heat treated of 20 minutes～4 hours, thereby form heat-curing resin layer.; stretching resin formed body is being taken off from stretching clamp or be fixed under the state of stretching clamp; the curable resin that contains thermal polymerization is coated on at least one side and above, forms heat-curing resin layer with above-mentioned temperature and time, can fix thus stretching resin formed body.And then, can also and use with the method for expressing as third method.The method can be as the householder method of the method for use stretching clamp.
As additive method; as required; in at least one side of the stretching resin formed body after stretching resin formed body or regelate before regelate, coating is containing the curable resin of Photoepolymerizationinitiater initiater and thermal polymerization state; irradiate the energy-ray of 400～10000mj and form curable resin layer; and; at the temperature of 25～200 DEG C, carry out the heat treated of 20 minutes～4 hours, make the slip of the acryloyl group in resin combination be roughly 100%.; stretching resin formed body is being unloaded from stretching clamp or be fixed under the state of stretching clamp; on the curable resin that contains Photoepolymerizationinitiater initiater and thermal polymerization is coated at least simultaneously; irradiate above-mentioned energy-ray and form the curable resin layer of at least 1 layer; and heat, stretching resin formed body can be fixed thus.The method can be as the householder method of the method for use stretching clamp.
For the curable resin of the one side of the stretching resin formed body after the stretching resin formed body or the regelate that are coated on before regelate, as long as thering is the transparency and weatherability and then can form the resin of the resin bed of Tg more than 200 DEG C in the time obtaining phase retardation film, be not particularly limited, preferably use the silicon resin composition of recording in JP 2006-89685 communique.That is, preferably use following silicon resin composition, that is, and with 5～40: 50～90: 0～30 polymerization ratio will be to use general formula [RSiO
3/2]
n(wherein, R is the organo-functional group with (methyl) acryloyl group, and n is 8,10 or 12) represents and in structural units, has silicones that the organic poly sesquisiloxane of cagelike structure is principal ingredient, in molecule, at least contains 1 use-R
3-CR
4=CH
2or-CR
4=CH
2(wherein, R
3represent alkylidene, alkylidene radical or-OCO-base, R
4represent hydrogen or alkyl) unsaturated group that represents and have and can carry out the oligomer with urethane bond of free-radical polymerized number-average molecular weight more than 2500 and can carry out free-radical polymerized unsaturated compound with aforementioned silicones and coordinate the silicon resin composition forming in addition with aforementioned silicones.
So, the scope that the phase retardation film obtaining by the present invention is 0～20nm at 100 DEG C of phase difference value variable quantities that carry out 10 hours phase retardation films after heat treated.Wherein, the phase difference value variable quantity of the phase retardation film after so-called heat treated, refer to the curable resin that regelate or coating contain Photoepolymerizationinitiater initiater and/or thermal polymerization and form light and/or heat-curing resin layer after measure immediately phase difference value, with the variable quantity between the phase difference value after 10 hours 100 DEG C of maintenances.In addition, in the situation of the preferred d=250 μ of phase retardation film of the present invention m, in the face at wavelength 550nm place, phase difference value Re is 5～150nm.In addition, phase difference value Re is obtained by following formula.In addition, said preferred phase difference value Re refers to the value obtaining 100 DEG C of chronometries that keep 10 hours herein.
Re＝(n
x-n
y)d
(n
x: the axial refractive index of x, n
y: the axial refractive index of y, d: thickness)
According to the present invention, even if also few excellent phase retardation film of the variable quantity that can obtain having phase differential after high transparent heating for example, can be suitable for the vehicle mounted touch panel purposes, the liquid crystal indicator purposes etc. that use under hot environment.
Embodiment
Embodiment etc. is below described, but the present invention is not limited to this.In addition, the silicones using in following embodiment and cage modle silicones are to obtain by the method shown in following synthesis example.
[synthesis example 1] (preparation of straight chain type silicones 1)
In reaction vessel, pack Isosorbide-5-Nitrae-bis-(hydroxyl dimetylsilyl) benzene 20g into, carry out vacuum drying.Stirring machine and tap funnel are installed, in reaction vessel, are packed into tetrahydrofuran (THF) 88ml as solvent, pack the pyridine 4ml as base catalyst into.In tap funnel, pack vinyl dimethyl dichlorosilane (DMCS) 12ml into, limit stirring reaction container, limit dripped with 15 minutes in ice bath.After dropping finishes, at room temperature stir 2 hours.Stir and drip dimethyldichlorosilane 0.5ml after 2 hours, stir 30 minutes.And then drip acrylic acid 2-hydroxy methacrylate 1.85ml, stir 1 hour.After stirring, with toluene 400ml dissolving.Reaction solution is washed and become after neutrality with saturated aqueous common salt, dewater with anhydrous magnesium sulfate.By anhydrous magnesium sulfate filtering, through the concentrated silicones 31g that obtains.The resin dissolves of gained, after toluene 5ml, is precipitated with methyl alcohol again, remove supernatant.Through the concentrated silicones 30g that obtains.This silicones is the micro white viscous liquid that can be dissolved in various organic solvents.
[synthesis example 2] (preparation of straight chain type silicones 2)
In reaction vessel, pack Isosorbide-5-Nitrae-bis-(hydroxyl dimetylsilyl) benzene 20g into, carry out vacuum drying.Stirring machine and tap funnel are installed, in reaction vessel, are packed into tetrahydrofuran (THF) 88ml as solvent, pack the pyridine 4ml as base catalyst into.In tap funnel, pack methacryl dimethyl dichlorosilane (DMCS) 12ml into, limit stirring reaction container, limit dripped with 15 minutes in ice bath.After dropping finishes, at room temperature stir 2 hours.Stir and drip dimethyldichlorosilane 0.5ml after 2 hours, stir 30 minutes.And then drip acrylic acid 2-hydroxy methacrylate 1.85ml, stir 1 hour.After stirring, with toluene 400ml dissolving.Reaction solution is washed and become after neutrality with saturated aqueous common salt, dewater with anhydrous magnesium sulfate.By anhydrous magnesium sulfate filtering, through the concentrated silicones 31g that obtains.The resin dissolves of gained, after toluene 5ml, is precipitated with methyl alcohol again, remove supernatant.By the concentrated silicones 30g that obtains.This silicones is the micro white viscous liquid that can be dissolved in various organic solvents.
[synthesis example 3] (preparation of cage modle silicones)
Obtain the method for the cage modle silicones on all silicon atoms with methacryl with reference to known synthetic method (JP 2006-089685 communique), carry out as follows.
Having in the reaction vessel of stirring machine, tap funnel and thermometer, pack 2-propyl alcohol (IPA) 40ml as solvent into, pack 5% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) as base catalyst into.In tap funnel, pack IPA 15ml and 3-methacryloxypropyl trimethoxy silane (the MTMS:Dow Corning Toray Silicone SZ6300 processed of company) 12.69g into, limit stirring reaction container, limit is at room temperature with the IPA solution that drips MTMS for 30 minutes.MTMS does not stir 2 hours after dripping and finishing heatedly.Stir after 2 hours, under reduced pressure solvent is removed, with toluene 50ml dissolving.Reaction solution is washed and become after neutrality with saturated aqueous common salt, dewater with anhydrous magnesium sulfate.By anhydrous magnesium sulfate filtering, through concentrated hydrolysate (silsesquioxane) 8.6g that obtains.This silsesquioxane is the colorless viscous liquid that can be dissolved in various organic solvents.
Then, in the reaction vessel with stirring machine, Dean-Stark moisture content determining device and condenser pipe, add silsesquioxane 20.65g obtained above, toluene 82ml and 10%TMAH aqueous solution 3.0g, heat water is heated up in a steamer gradually.And then, be heated to 130 DEG C, make toluene under reflux temperature, carry out condensation reaction again.The temperature of reaction solution is now 108 DEG C.After refluxing toluene, stir 2 hours, then make reaction finish.Reaction solution is washed and become after neutrality with saturated aqueous common salt, dewater with anhydrous magnesium sulfate.By anhydrous magnesium sulfate filtering, through concentrated cage modle silicones (potpourri) 18.77g obtaining as object.The cage modle silicones of gained is the colorless viscous liquid that can be dissolved in various organic solvents.
The cage modle silicones obtaining by aforementioned condensation reaction again carries out carrying out quality analysis after liquid chromatography separation, results verification with the molecular ion peak of ammonium radical ion, component ratio is T8: T10: T12: " other " are about 2: 4: 1: 3, can be confirmed to be the silicones taking cagelike structure as principal ingredient.In addition, so-called T8, T10 and T12, refer at [RSiO
3/2]
nin represent successively the silicones (R is methacryl) of n=8, n=10 and n=12.
[synthesis example 4] (preparation of oligourethane)
The method that makes organic isocyanate and polyol reaction and obtain polyurethane, with reference to known synthetic method (Unexamined Patent 6-166737 communique), is carried out as follows.
Using the ratio of components ratio of 4: 3 make as the isophorone diisocyanate of organic isocyanate, with by 2,2-dimethyl-1, ammediol, 1, the polyol that 4-cyclohexanedimethanol and 6-caprolactone form as 1: 1: 1 taking mol ratio reacts, and make acrylic acid-2-hydroxyl ethyl ester reaction, obtain thus thering is the urethane acrylate oligomer 1 (number-average molecular weight 3800) of propenyl as object at two ends.
[embodiment 1]
Using the straight chain type silicones 1 obtaining (100 weight portion), mix as the 1-hydroxycyclohexylphenylketone (1 weight portion) of Photoepolymerizationinitiater initiater and as the dicumyl peroxide (5 weight portion) of thermal polymerization, obtain silicon resin composition in above-mentioned synthesis example 1.
Then, use excellent painting machine by silicon resin composition curtain coating obtained above (cast) to the quartz glass of thick 1mm and to make thickness be 0.1mm, use the ultrahigh pressure mercury lamp of 333W/cm with 2000mJ/cm
2cumulative exposure amount (365nm conversion) make it curing, obtain having the flaky resin formed body of specific thickness.Reaction rate is now < 2%.In table 1, provide composition and exposure and the reaction rate of the resin combination of this embodiment 1.
From flaky resin formed body obtained above, cut out the small pieces of 25mm × 70mm, use biaxial stretch-formed device (well unit makes made), under the condition of 25 DEG C of temperature, draw speed 5mm/min., implement uniaxial tension at length direction, obtain+18% stretched film (stretching resin formed body).Then, the heat treated that uses small size vacuum electric furnace (beautiful made with making) to carry out 200 DEG C, 1 hour to each fixing fixture, then cool to room temperature, obtain+14% stretched film (phase retardation film).The thickness of stretched film is 133 μ m, the phase difference value Re=(n in face
x-n
y) d is+9nm.It should be noted that n
xthe axial refractive index of x, n
ythat the axial refractive index of y, d are thickness.In addition, measure Re value (phase difference value) and the transmissivity after 100 DEG C of heating heat resistant test (heat treated) of 10 hours by gained phase retardation film.Show the result in table 2.
[embodiment 2]
The weight portion and cumulative exposure amount of the mix proportion providing except use table 1, all the other obtain resin-formed body similarly to Example 1.
From flaky resin formed body obtained above, cut out the small pieces of 50mm × 70mm, use biaxial stretch-formed device (well unit makes made), under the condition of 25 DEG C of temperature, draw speed 5mm/min., implement uniaxial tension at length direction, obtain+15% stretched film (stretching resin formed body).
Then, by the cage modle silicones obtaining in above-mentioned synthesis example 3 (30 weight portion), tetrahydro-dicyclopentadiene base diacrylate (65 weight portion), urethane acrylate oligomer (5 weight portion), and mix as the 1-hydroxycyclohexylphenylketone (2.5 weight portion) of Photoepolymerizationinitiater initiater, obtain after the resin combination of resin bed formation use, on quartz glass, place obtained above+15% stretched film, using excellent painting machine that this resin bed formation resin combination curtain coating (cast) is gone up and make thickness to one side is 50 μ m, use the ultrahigh pressure mercury lamp of 333W/cm, with 2000mJ/cm
2cumulative exposure amount (365nm conversion) make it curing.And then on remaining, also this resin bed of curtain coating (cast) forms with resin combination and to make thickness be 50 μ m, uses the ultrahigh pressure mercury lamp of 333W/cm, with 3000mJ/cm
2cumulative exposure amount (365nm conversion) make it curing, obtain the phase retardation film of the embodiment 2 with resin bed.The thickness of this phase retardation film is 200 μ m, the phase difference value Re=(n in face
x-n
y) d is+34nm.In addition, measure Re value (phase difference value) and the transmissivity after 100 DEG C of heating heat resistant test (heat treated) of 10 hours by gained phase retardation film.Show the result in table 2.
[comparative example 1]
Except resin combination being made as to the weight portion and cumulative exposure amount of the mix proportion shown in table 1, all the other obtain resin-formed body similarly to Example 1.
From the resin-formed body of gained, cut out the small pieces of 25mm × 70mm, use biaxial stretch-formed device (well unit makes made), under the condition of temperature 60 C, draw speed 5mm/min., implement uniaxial tension at length direction, obtain+10% stretched film.The heat treated that uses heated-air circulation oven (Fushan Mountain industry system) to carry out 180 DEG C, 30 minutes to each fixing fixture, obtains+5% stretched film.The thickness of stretched film is 224 μ m, the phase difference value Re=(n in face
x-n
y) d is+13nm.But, carry out heat resistant test, result Re value (phase difference value) is 0nm, the performance of phase retardation film disappears.
Various tests in above-described embodiment and comparative example, carry out with being determined as follows.
(heat resistant test)
Use TMA determinator EXSTAR6000 (SII system) to keep 10 hours at 100 DEG C.
(mensuration of the length of delay Re of phase retardation film)
Use measuring difference of phases device NPDM-1000 (Nikon system) to measure.The phase difference value of λ 550nm is shown in to table 2.
(mensuration of length of delay Re variable quantity)
Calculated the poor of the Re value of carrying out after aforementioned heat resistant test by the Re value before heat resistant test.
In addition, in following table 1, dummy suffix notation is expressed as follows implication.
A: straight chain type silicones 1
B: straight chain type silicones 2
C: cage modle silicones
D: tetrahydro-dicyclopentadiene base diacrylate (the LIGHTACRYLATE DCP-A processed of common prosperity society chemistry (strain))
E: urethane acrylate oligomer
F:1-hydroxycyclohexylphenylketone
G: dicumyl peroxide (Japanese grease (strain) PERCUMYL D processed)
Table 1
Table 2
Claims (14)
1. a phase retardation film, it is characterized in that, to make resin combination solidify the phase retardation film forming, the scope that is 0～20nm at 100 DEG C of phase difference value variable quantities that carry out 10 hours phase retardation films after heat treated, described resin combination contains the represented number-average molecular weight of (1) following general formula (1) silicones and (2) Photoepolymerizationinitiater initiater and/or (3) thermal polymerization in 1000～80000 scopes
In formula, X is the divalent group with at least one silicon atom and at least one aromatic group, R
1the organo-functional group with (methyl) acryloyl group, R
2represent to have replacement or unsubstituted aromatic rings that the organo-functional group of (methyl) acryloyl group or vinyl, aliphatic hydrocarbon that carbon number is 1～25, replacement that carbon number is 6～15 or unsubstituted alicyclic ring or carbon number are 6～15, l=1, m=1～3, n are 2～290.
2. phase retardation film as claimed in claim 1, is characterized in that, with respect to total 100 weight portions of resin combination, contains (2) Photoepolymerizationinitiater initiater 0.1～3 weight portion.
3. phase retardation film as claimed in claim 1, is characterized in that, with respect to total 100 weight portions of resin combination, contains (3) thermal polymerization 0.1～10 weight portion.
4. phase retardation film as claimed in claim 1, it is characterized in that, with respect to total 100 weight portions of resin combination, contain (2) Photoepolymerizationinitiater initiater 0.01～1 weight portion and contain (3) thermal polymerization 0.01～10 weight portion.
5. the phase retardation film as described in any one in claim 1～4, is characterized in that, carrying out 10 hours thickness d=250 μ m after heat treated phase difference value in the face at wavelength 550nm place at 100 DEG C is 5～150nm.
6. the phase retardation film as described in any one in claim 1～4, is characterized in that, at least on one side, having more than 1 layer by glass transition temperature Tg is the resin bed that more than 200 DEG C light and/or heat-curing resin form.
7. phase retardation film as claimed in claim 5, is characterized in that, at least on one side, having more than 1 layer by glass transition temperature Tg is the resin bed that more than 200 DEG C light and/or heat-curing resin form.
8. the manufacture method of a phase retardation film, it is characterized in that, use resin combination to manufacture phase retardation film, described resin combination contains the represented number-average molecular weight of (1) following general formula (1) silicones and (2) Photoepolymerizationinitiater initiater and/or (3) thermal polymerization in 1000～80000 scopes
In formula, X is the divalent group with at least one silicon atom and at least one aromatic group, R
1the organo-functional group with (methyl) acryloyl group, R
2represent to have replacement or unsubstituted aromatic rings that the organo-functional group of (methyl) acryloyl group or vinyl, aliphatic hydrocarbon that carbon number is 1～25, replacement that carbon number is 6～15 or unsubstituted alicyclic ring or carbon number are 6～15; l=1, m=1～3, n are 2～290
With at least 1 supporting mass supporting resin combination, the one-step solidification of the unsaturated group minimizing 0.1%～50% of above-mentioned by making (1) composition obtains after resin-formed body, this resin-formed body is cut into regulation shape and is fixed on stretching clamp, after stretching with the scope of extensibility 5%～700% in any direction, obtain stretching resin formed body, under the state that this stretching resin formed body is fixed on to stretching clamp, further heat and/or irradiation energy ray and make it regelate, then cool to room temperature.
9. the manufacture method of phase retardation film as claimed in claim 8, is characterized in that, the method for one-step solidification is from the opposition side of supporting side or supporting mass or irradiates the energy-ray illuminating method of the energy-ray of 300～6000mj from these both sides.
10. the manufacture method of phase retardation film as claimed in claim 8, is characterized in that, the method for one-step solidification is the heating means that heat at 25～200 DEG C.
The manufacture method of 11. phase retardation films as claimed in claim 8, is characterized in that, the method for stretching is uniaxial tension orientation.
The manufacture method of 12. phase retardation films as claimed in claim 8, it is characterized in that, the curable resin that at least one side of the stretching resin formed body after stretching resin formed body or regelate before regelate, coating contains Photoepolymerizationinitiater initiater, irradiate the energy-ray of 1000～20000mj, thereby form light-cured resin layer.
The manufacture method of 13. phase retardation films as claimed in claim 8, it is characterized in that, the curable resin that at least one side of the stretching resin formed body after stretching resin formed body or regelate before regelate, coating contains thermal polymerization, at the temperature of 25～200 DEG C, carry out the heat treated of 20 minutes～4 hours, thereby form heat-curing resin layer.
The manufacture method of 14. phase retardation films as claimed in claim 8, it is characterized in that, the curable resin that at least one side of the stretching resin formed body after stretching resin formed body or regelate before regelate, coating contains Photoepolymerizationinitiater initiater and thermal polymerization, irradiate the energy-ray of 400～10000mj, and at the temperature of 25～200 DEG C, carry out the heat treated of 20 minutes～4 hours, thereby form light and heat curable resin layer.
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| JP2009052699A JP5457051B2 (en) | 2009-03-05 | 2009-03-05 | Retardation film and method for producing the same |
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| KR102511899B1 (en) * | 2015-03-13 | 2023-03-20 | 미쯔비시 케미컬 주식회사 | Optical film and its manufacturing method |
| CN113211700A (en) * | 2021-03-22 | 2021-08-06 | 鞍钢冷轧钢板（莆田）有限公司 | Fingerprint-resistant liquid film forming method containing double photosensitive resin frameworks |
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| US5346980A (en) * | 1992-04-14 | 1994-09-13 | Minnesota Mining And Manufacturing Company | Crosslinkable silarylene-siloxane copolymers |
| JP2001337223A (en) * | 2000-05-26 | 2001-12-07 | Hitachi Chem Co Ltd | Method for using optical wavelength plate utilizing polymer resin film |
| JP4078138B2 (en) * | 2002-07-10 | 2008-04-23 | 株式会社神戸製鋼所 | Photocurable resin coating composition having antifouling property and easy cleaning property, and cured coating film |
| JP4256756B2 (en) * | 2002-09-30 | 2009-04-22 | 新日鐵化学株式会社 | Method for producing cage-type silsesquioxane resin having functional group |
| US7385017B2 (en) * | 2003-03-27 | 2008-06-10 | Nippon Steel Chemical Co., Ltd. | Silicone resin compositions and molded articles thereof |
| JP4372065B2 (en) * | 2004-09-09 | 2009-11-25 | 信越化学工業株式会社 | Solvent-free polyimide silicone resin composition and cured resin film thereof |
| JP4409397B2 (en) * | 2004-09-27 | 2010-02-03 | 新日鐵化学株式会社 | Silicone resin composition and molded body |
| KR101209049B1 (en) * | 2004-12-24 | 2012-12-07 | 스미또모 가가꾸 가부시끼가이샤 | Photosensitive resin and thin film panel comprising pattern made of the photosensitive resin and method for manufacturing the thin film panel |
| TWI431375B (en) * | 2007-03-28 | 2014-03-21 | Nippon Steel & Sumikin Chem Co | A retardation film and a retardation film laminate, and a method of manufacturing the same |
| TW201000491A (en) * | 2008-03-28 | 2010-01-01 | Nippon Steel Chemical Co | Silanol-group-containing curable cage-type silsesquioxane compound, cage-structure-containing curable silicone copolymer, processes for producing these, and curable resin composition |
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| KR20100100600A (en) | 2010-09-15 |
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